CN102658137B - Cerium-zirconium-palladium nano powder catalyst and preparation and application thereof - Google Patents
Cerium-zirconium-palladium nano powder catalyst and preparation and application thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011858 nanopowder Substances 0.000 title claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000006698 induction Effects 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 230000008020 evaporation Effects 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims abstract description 3
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 238000001338 self-assembly Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000779 smoke Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 230000001603 reducing effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 47
- 229910000510 noble metal Inorganic materials 0.000 abstract description 16
- 239000007789 gas Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000003546 flue gas Substances 0.000 abstract description 11
- 230000008030 elimination Effects 0.000 abstract description 7
- 238000003379 elimination reaction Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 238000004523 catalytic cracking Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 36
- 239000006104 solid solution Substances 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000010718 Oxidation Activity Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004231 fluid catalytic cracking Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 229910004625 Ce—Zr Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000000935 solvent evaporation Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JIZGEMUCLDTNAL-UHFFFAOYSA-N CO.FCC Chemical compound CO.FCC JIZGEMUCLDTNAL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a preparation method of a cerium-zirconium-palladium nano powder catalyst; dissolving a cerium source and a zirconium source in absolute ethyl alcohol, and adding a P123 template agent to obtain sol; adding palladium nitrate; keeping constant temperature and humidity, the temperature is 35 ℃, the relative humidity is 40%, and evaporation induction is carried out; forming gel, and drying at 100 deg.C; roasting at 400 ℃ for 4 hours, wherein the heating rate is 1 ℃ per minute; the atomic mol ratio of cerium to zirconium is 8: 2; the loading amount of palladium is 0.1-5 wt%; the ratio of the cerium source, the zirconium source and the absolute ethyl alcohol to the P123 is 10mmol, 20ml and 1 g; the catalyst is suitable for catalytic elimination of CO in flue gas discharged by a catalytic cracking catalyst regeneration device and motor vehicle tail gas, has the advantages of large specific surface area, uniform distribution of noble metal active components, high catalytic activity, high thermal stability and simple and convenient synthesis method, can greatly reduce the complete catalytic conversion temperature of CO, saves the consumption of noble metals and reduces the catalyst cost.
Description
Technical field
The present invention relates to a kind of nano-powder pattern cerium zirconium palladium catalyst and preparation thereof, and this catalyst system reduces the purposes of CO complete catalysts oxidation temperature aspect in industrial smoke and motor-vehicle tail-gas.
Background technology
Industrial production is discharged and in flue gas, is had a large amount of CO.FCC (fluid catalytic cracking) is one of main method of oil plant production light-end products.In the regenerative process of FCC catalyst, due to the imperfect combustion of coke, in regenerated flue gas, contain the carbon monoxide (CO) of 6-10v%, be one of primary pollution source of oil plant.Meanwhile, CO further burns and becomes CO
2time can emit a large amount of heats, if made full use of, will not cause a large amount of thermal waste.The use of combustion adjuvant not only can make CO content in flue gas reduce, and reduces atmosphere pollution, and temperature that can stable regeneration device, avoids regenerator to damage and catalyst failure, saves equipment investment, improves regeneration quality and the fume afterheat utilization ratio of catalyst.At present, the FCC regenerated flue gas of most of oil plant adopts take precious metals platinum catalyst as main CO combustion adjuvant, has obtained remarkable result.But platinum catalyst is not only expensive, and the sulfide in flue gas and nitride catalyst can be converted into oxysulfide (SOx) and nitrogen oxide (NOx), thereby cause the corrosion of regenerator and produce the new source of atmospheric pollution.Therefore, develop a kind of new non-catalytic material, not only can effectively make CO completing combustion, and can impel the transfer of sulphur and the reduction of nitrogen oxide, thereby eliminate the pollution of regenerated flue gas to environment, there is important Research Significance and application prospect.
Be no matter to contain a large amount of CO in the flue gas that discharges of motor-vehicle tail-gas or refinery device, environment and common people's health are caused to very big harm, exploitation effective catalyst is to eliminate the strongest approach that CO reduces its discharge.The noble metals such as Pt, Rh, Pd have good catalytic oxidation elimination activity to CO and volatile hydrocarbon, yet Pt, Rh source is relatively rare, price is relatively costly.Therefore, Pd catalyst is subject to researcher's extensive concern in recent years.CeO
2because of Ce
4+/ Ce
3+there is good reversible conversion and there is good redox property and store oxygen ability (OSC), but at high temperature easily reuniting, Zr
4+part doping can to a certain degree improve its heat endurance and redox property.In addition preparation method has vital impact to catalyst performance.Therefore the good oxidation reducing property of cerium sill and the excellent activity of Pd can combine effectively, adopt accordingly specific preparation technology to be expected to synthesize active good catalyst.
As everyone knows, the preparation method of catalyst has vital impact to its performance.All there is larger difference in all many-sides such as valence state, structure, patterns in the catalyst of different preparation method's synthesizeds, thereby causes the difference of physicochemical properties aspect, and then cause the variation of catalytic performance.The metal active constituent loading method extensively adopting at present mainly contains infusion process, coprecipitation, deposition-precipitation method, ion-exchange etc.
A kind of preparation method of palladium catalyst carried by composite oxides of Ce-Zr is disclosed in Chinese patent CN1695799, the preparation method of this palladium catalyst carried by composite oxides of Ce-Zr, cerium and zirconium and citric acid are made into mixed solution, take fibrous matter as template and combustion carrier, dipping mixed solution, wherein fibrous matter comprises analytical paper, printing paper, paper pulp, cotton, absorbent cotton and cellulose etc.; The fibrous matter soaking is dried, and logical oxygen roasting, makes cerium zirconium compound oxide; Preparation palladium solution, is distributed to the cerium zirconium compound oxide making in palladium solution; Take alkali as precipitating reagent, precipitating reagent is joined in the soluble metal salting liquid that has mixed cerium zirconium compound oxide, making this pH value of solution is 9～12, ageing, suction filtration, deionized water washing; Dry roasting in air; Under hydrogen atmosphere, reduce, make palladium catalyst carried by composite oxides of Ce-Zr.The present invention is simple, and product surface area is large, has that initiation temperature is low, catalytic efficiency is high, the feature of heat resistant.But this invention operation process is complicated, and wherein influence factor is a lot of, carrier and active component yet do not realize and organically combining.
Chinese patent CN1548368 has reported at catalyst for selective oxidation of CO under hydrogen-enriched condition.It is a kind of for catalyst for selective oxidation of CO under hydrogen-enriched condition that this invention provides, and uses the noble metal of small amount, obtains the oxidation activity of higher low temperature carbon monoxide with selective.This catalyst consists of noble metal component and other metal components of being supported on porous inorganic thing carrier.It is characterized in that, aforementioned noble metal component can be at least one in following noble metal group, and aforementioned other metal components can be at least one in following other metal groups.Noble metal group: platinum, ruthenium, gold, rhodium, palladium; Other metal groups: iron, titanium, zirconium, barium, tin, tungsten, zinc, molybdenum, cerium, lanthanum.Catalyst bullion content of the present invention is low, and can effectively be applied to the selective oxidation of carbon monoxide under hydrogen rich gas atmosphere.The active initial temperature of catalyst of the present invention is low, and serviceability temperature wide ranges can effectively be worked between 80 ℃-180 ℃.Catalyst of the present invention in effective operating temperature interval oxygen selectively can be up to 80-90%,, when effectively removing carbon monoxide, the consumption of hydrogen is few.But this invention depends on the use of hydrogen, in process, there is certain complexity.Therefore, the research and development of new catalyst system are still very important.
Object of the present invention concentrates on the low temperature elimination to CO.Employing original position supports and the method for structure confinement can well realize being uniformly distributed of metal component and stability at high temperature.What in the present invention, adopt is that collosol and gel-evaporation induction self assembly (EISA)-original position supports method one-step synthesis x wt%Pd/Ce
xzr
1-Xo
2catalyst.This synthetic thinking has the advantage of himself uniqueness, has realized the combination of carrier part and active component part, has stronger interaction, has formed solid solution structure.
Summary of the invention
The object of this invention is to provide a kind of cerium zirconium palladium nano powder catalyst.This catalyst is high to the CO catalysis elimination activity in industrial smoke, significantly reduces the complete catalyzed conversion temperature of CO, have that reference area is large simultaneously, the high and low noble metal dosage of heat endurance, Active components distribution evenly and the advantage such as simple synthetic method.
The present invention also provides the preparation method of cerium zirconium palladium nano powder catalyst, by the optimum organization to synthetic method, design, obtain granule-morphology homogeneous, there is the simple relatively inexpensive noble metal catalyst of high activity, synthetic method of special solid solution composite oxides structure.
The present invention also provides and has utilized the application aspect CO complete catalysts oxidation elimination temperature in reducing motor-vehicle tail-gas and industrial smoke of described catalyst.
First the present invention provides cerium zirconium palladium nano powder catalyst, is to take the solid solution catalyst that ,Ba source, ,Gao source, cerium source is precursor one-step synthesis.The cerium Zirconium oxide wherein forming serves as carrier part, and palladium oxide serves as active component.In this noble metal catalyst, the atomic molar ratio of cerium zirconium is 8: 2, and the loading of palladium is 0.1～5wt% (0.1wt%, 0.2wt%, 0.5wt%, 1.0wt%, 2.0wt%, 5.0wt%).
According to nano-powder pattern solid solution composite oxide catalysts provided by the invention, wherein, carrier and active component are not significantly distinguished, and cerium Zirconium oxide serves as carrier, and palladium oxide serves as active component.In one-step synthesis process, adopting respectively cerous nitrate, zirconium oxychloride, palladium nitrate is precursor solution, and P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer) is template, the system that the absolute ethyl alcohol of take is solvent.Presoma is attached in the template forming through pervaporation induction assembling through hydrolysis.System has collosol state originally to transfer gel state to after the process of solvent evaporation, then through super-dry, in air, roasting obtains having the nano-powder solid solution cerium zirconium palladium catalyst of the nano-powder pattern of homogeneous particle diameter.
In the present invention, ,Ba source, ,Gao source, cerium used source is respectively Ce (NO
3) 6H
2o, ZrOCl
28H
2o, Pd (NO
3) 2H
2o.Described catalyst can be expressed as x wt%Pd/Ce
0.8zr
0.2o
2, x=0.1 wherein, 0.2,0.5,1.0,2.0,5.0.
Catalyst provided by the invention is a kind of solid solution composite oxide catalysts, and metal oxide containing precious metals is active component.Whole caltalyst architecture homogeneous, has high chemical stability.Experimental result shows, the promotion that cerium Zirconium oxide and the Nano Solid Solution of palladium formation are favourable palladium dispersed, and it is existed with oxide form, prevented its sintering at high temperature, thereby greatly improved CO oxidation activity and stability.The complete catalysts oxidation temperature of CO is reduced within the scope of 50～150 ℃, the elimination requirement that causes a large amount of CO to pollute while meeting motor vehicle cold start (200 ℃ of <).
The present invention also provides the preparation method of cerium zirconium palladium nano powder catalyst, and it comprises:
,Gao source, cerium source is dissolved in a certain amount of absolute ethyl alcohol by certain mole of proportioning, adds a certain amount of P123 template simultaneously, in 35 ℃ of water-baths, strong stirring 2 hours, obtains the micro-yellow sol of transparent and homogeneous.Press certain mass than palladium source, continue strong stirring 8 hours, with culture dish, be transferred in constant temperature and humidity drying case, controlling temperature is 35 ℃, and relative humidity is 40%, the self assembly of carrying out solvent evaporation and inducing P123 in this environment, evaporation induction time continues to form gel after 48 hours, and then in 100 ℃ of conditions dry 24 hours, finally roasting 4 hours under 400 ℃ of conditions, heating rate is 1 ℃ per minute.
In the present invention, dissolving is stirred and is evaporated very key of the temperature conditions of induction and the self assembly of template.P123 is a kind of organic polymer surfactant, after dissolving, when concentration surpasses critical micelle concentration (cmc), starts the micella that self assembly forms certain pattern in solvent, and along with the variation of concentration, micella pattern can change.In this course, strict temperature conditions is most important, because it is directly connected to the whole process of macromolecular dissolving and self assembly.The micella of the certain pattern forming plays the effect of template after solidifying to form gel, forms certain space support structure, obtains the catalyst with dispersing nanometer morphology microstructure after calcination process.
In this case, the atomic molar proportioning in He Gao source, cerium source is 8: 2, and Jia Gao source, cerium source, absolute ethyl alcohol and P123 three's typical synthetic ratio is 10mmol: 20ml: 1g.
In this case, traditional sol-gal process and evaporation induction self-assembling method comparatively advanced in nanometer is synthetic are organically combined, and realized the one-step synthesis of noble metal catalyst, and be different from the synthetic thinking of most catalyst.
The catalyst of preparing in the present invention is eliminated and demonstrated good catalytic activity for CO catalysis, and the complete conversion temperature of CO significantly reduces, many in the scope of 50～150 ℃.Experimental result also shows, this caltalyst ties up to after the high temperature ageing of 800 ℃, and catalytic activity substantially remains unchanged and has superior high temperature resistance stability.
The invention provides in a word a kind of cerium zirconium palladium catalyst.Described catalyst is by collosol and gel, in conjunction with the method for evaporation induction self assembly, to follow the noble metal composite oxide catalyst of the thought one-step synthesis that original position supports.This catalyst is applicable to the catalysis that motor-vehicle tail-gas and chemical production device discharge CO in flue gas and eliminates, there is the advantages such as specific area is large, the free of losses of noble metal active uniform component distribution, catalytic activity is high, heat endurance is high, simple synthetic method, can significantly reduce the complete catalyzed conversion temperature of CO, save noble metal dosage, reduce catalyst cost.The present invention has good effect to the low temperature elimination of CO in motor-vehicle tail-gas and industrial discharge flue gas, and this has great meaning for atmospheric environment protection.
Accompanying drawing explanation
Fig. 1 a is that Pd loading is 0.1% 0.1wt%Pd/Ce
0.8zr
0.2o
2the TEM photo of catalyst.
Fig. 1 b is that Pd loading is 0.2% 0.1wt%Pd/Ce
0.8zr
0.2o
2the TEM photo of catalyst.
Fig. 1 c is that Pd loading is 0.5% 0.1wt%Pd/Ce
0.8zr
0.2o
2the TEM photo of catalyst.
Fig. 1 d is that Pd loading is 1.0% 0.1wt%Pd/Ce
0.8zr
0.2o
2the TEM photo of catalyst.
Fig. 1 e is that Pd loading is 2.0% 0.1wt%Pd/Ce
0.8zr
0.2o
2the TEM photo of catalyst.
Fig. 1 f is that Pd loading is 5.0% 0.1wt%Pd/Ce
0.8zr
0.2o
2the TEM photo of catalyst.
Fig. 2 a is different Pd loading x wt%Pd/Ce
0.8zr
0.2o
2(x=0,0.1,0.2,0.5,1.0,2.0,5.0) catalyst series XRD spectra.
Fig. 2 b is the different Pd loading x wt%Pd/Ce after amplifying
0.8zr
0.2o
2(x=0.1,0.2,0.5,1.0,2.0,5.0)
Catalyst series XRD spectra.
Fig. 3 a is different Pd loading x wt%Pd/Ce
0.8zr
0.2o
2the CO oxidation activity of catalyst.
Fig. 3 b is 800 ℃ of aging rear xwt%Pd/Ce
0.8zr
0.2o
2the CO oxidation activity of catalyst.
The specific embodiment
Embodiment 1:
Take respectively Ce (NO
3) 6H
2o 3.4740g, ZrOCl
28H
2o 0.6445g is dissolved in 20ml absolute ethyl alcohol, adds 1g P123 template simultaneously, is placed in 35 ℃ of water-baths, and strong stirring 2 hours obtains the micro-yellow sol of transparent and homogeneous.Then add 0.0041g Pd (NO
3) 2H
2o (supporting according to 0.1wt%Pd), continue strong stirring 8 hours, with culture dish, be transferred in constant temperature and humidity drying case, controlling temperature is 35 ℃, and relative humidity is 40, the self assembly of carrying out solvent evaporation and inducing P123 in this environment, evaporation induction time continues to form gel after 48 hours, and then in 100 ℃ of conditions dry 24 hours, finally roasting 4 hours under 400 ℃ of conditions, heating rate is 1 ℃ per minute.The cerium zirconium palladium solid solution that obtains nano-powder pattern, Fig. 1 a～f provides the TEM photo of this catalyst, and catalyst has all formed nano-powder; On photo, can not distinguish obvious difference carrier and active component, show to have formed solid solution.X-ray diffraction (XRD) shows that this catalyst is really for having the solid solution of fluorite phase Emission in Cubic structure, even if because there is not belonging to Pd in the characteristic diffraction peak of PdO after amplifying Y-axis yet, and at Pd, support 2 θ angles of rear catalyst on carrier and be offset to high angle direction, show that Pd has entered the lattice of carrier, further proof has formed solid solution structure.Fig. 2 a, b provides the XRD spectra of this catalyst.
Embodiment 2:
Preparation condition and preparation procedure are with example 1, just by Pd (NO
3) 2H
2the addition of O changes respectively 0.0081,0.0203,0.0406,0.0813 into, 0.2032g, makes the loading of Pd be respectively 0.2wt%, 0.5wt%, 1.0wt%, 2.0wt%, 5.0wt%.
Embodiment 3:
Adopt transmission electron microscope (TEM) observation post's Kaolinite Preparation of Catalyst (a) 0.1wt%Pd/Ce
0.8zr
0.2o
2, (b) 0.2wt%Pd/Ce
0.8zr
0.2o
2, (c) 0.5wt%Pd/Ce
0.8zr
0.2o
2, (d) 1.0wt%Pd/Ce
0.8zr
0.2o
2(e) 2.0wt%Pd/Ce
0.8zr
0.2o
2, (f) 5.0wt%Pd/Ce
0.8zr
0.2o
2pattern.Adopt the crystal phase structure of X-ray diffraction (XRD) analysis of catalyst, and employing thanks to crystallite dimension and the cell parameter of strangling formula calculating catalyst.
TEM result by sample in Fig. 1 a～f can find out, prepared catalyst granules particle diameter is all at 5～10nm, and particle diameter is even, has nano-powder pattern, has larger gap between particle, can be the larger interface of providing of catalytic reaction.
The half-peak breadth β of the corresponding diffraction maximum of sample thief (111) crystal face, adopts Scherrer formula: D=0.89 λ/(β cos θ) to calculate x wt%Pd/Ce
0.8zr
0.2o
2the crystallite dimension of catalyst series, wherein λ=0.15406nm.Table 1 is crystallite dimension result of calculation.Data show,
The computational methods of cell parameter are as follows, by Bragg equation 2dsin θ=λ, calculate interplanar distance d, cell parameter a=d*N (quadratic sum that N is the indices of crystallographic plane).This method is applicable to the calculating of cubic structure structure cell.
The different Pd loading of table 1 x wt%Pd/Ce
0.8zr
0.2o
2the crystallite dimension of (x=0,0.1,0.2,0.5,1.0,2.0,5.0) catalyst series
From table 1, to the result of calculation of crystallite dimension and lattice parameter, can find out Ce
0.8zr
0.2o
2after load P d, lattice parameter changes to some extent, and along with the increase lattice parameter of Pd load capacity reduces to be all less than gradually
corresponding to standard cube type CeO
2lattice parameter a), show that lattice has certain contraction.Therefore in system, be due to the doping of Zr, Pd, to have caused the polycondensation (Zr of lattice
4+ionic radius is 0.084nm, Pd
2+ionic radius is 0.086nm, is all less than Ce
4+ionic radius 0.097nm) formed cerium zirconium palladium solid solution.
Embodiment 4:
Catalyst performance evaluation:
Adopt atmospheric fixed bed microreactor laboratory evaluation device, evaluate the catalytic activity of the synthetic catalyst of the present invention to CO oxidation reaction in FCC regenerated flue gas.Reactor adopts the quartz ampoule of internal diameter 6mm, the temperature reaction of automatic temperature control instrument control program, and programming rate is 5 ℃/min.Take the catalyst of 100mg, be filled in the constant temperature zone of reaction tube, prepare in advance on request reacting gas, gas composition is: CO:10000ppm, O
2: 10v%, Ar is balanced gas; Gas flow is 50ml/min.The SP-3420 gas chromatograph that experimental result is produced through Beijing Analytical Instrument Factory detects, FID hydrogen flame ionization detector, and FID connects with methanator, chromatographic column adopting 5A molecular sieve packed column (separated O
2, N
2, CO) and Porapak N packed column (separation of C O, CO
2and C
2h
2), methanator operating temperature is 380 ℃.
The catalyst of preparing in this case is carried out to the evaluation of CO oxidation activity, and experimental result is as table 2, table 3.
The different Pd loading of table 2 x wt%Pd/Ce
0.8zr
0.2o
2the activity data of catalyst
Table 3800 ℃ aging rear different Pd loading x wt%Pd/Ce
0.8zr
0.2o
2the activity data of catalyst
By the experimental result of table 2, table 3, can find out that this catalyst series has good CO oxidation activity, wherein active best for loading be the catalyst of 1wt% and 2wt%, and after 800 ℃ of roastings are aging, catalyst activity is still maintained and even obtains certain raising, show that the catalyst in the present invention not only has high activity and has good heat endurance, has solved the problem of noble metal catalyst poor heat stability well.
Claims (4)
1. a preparation method for cerium zirconium palladium nano powder catalyst, is characterized in that:
(1) ,Gao source, cerium source is dissolved in absolute ethyl alcohol, adds P123 template, be placed in water-bath, at 35 ℃, strong stirring dissolves 2 hours, obtains transparent and homogeneous colloidal sol;
(2) add palladium nitrate, continue strong stirring 8 hours;
(3) with culture dish, be transferred in constant temperature and humidity drying case, solvent evaporates and induces the self assembly of P123, and process keeps constant temperature and humidity, 35 ℃ of temperature, and relative humidity 40%, evaporation induction time continues 48 hours; After evaporation induction, form gel, dry, baking temperature is 100 ℃, continues 24 hours; Roasting obtains catalyst, and catalyst roasting condition is 400 ℃ of stops 4 hours, and heating rate is 1 ℃ per minute;
Cerium is 8: 2 with the atomic molar ratio of zirconium; The loading of palladium is 0.1～5wt%;
Jia Gao source, cerium source, absolute ethyl alcohol and P123 three's proportioning is 10mmol: 20ml: 1g.
2. the preparation method of cerium zirconium palladium nano powder catalyst as claimed in claim 1, is characterized in that: the ,Ba source, ,Gao source, precursor cerium source adopting is respectively six nitric hydrate ceriums, eight hydration zirconium oxychlorides, two nitric hydrate palladiums.
3. a cerium zirconium palladium nano powder catalyst, is characterized in that: prepared by preparation method according to claim 1.
4. an application for cerium zirconium palladium nano powder catalyst claimed in claim 3, is characterized in that: for reducing the complete catalyzed conversion temperature of CO in motor-vehicle tail-gas and industrial smoke, under its effect, CO is oxidized to CO
2eliminate.
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